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WO2013146482A1 - Composition de revêtement dur et composition de formation d'une couche anti-adhérente à indice de réfraction élevé - Google Patents

Composition de revêtement dur et composition de formation d'une couche anti-adhérente à indice de réfraction élevé Download PDF

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Publication number
WO2013146482A1
WO2013146482A1 PCT/JP2013/057891 JP2013057891W WO2013146482A1 WO 2013146482 A1 WO2013146482 A1 WO 2013146482A1 JP 2013057891 W JP2013057891 W JP 2013057891W WO 2013146482 A1 WO2013146482 A1 WO 2013146482A1
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Prior art keywords
film
layer
acrylate
refractive index
hard coat
Prior art date
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Ceased
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PCT/JP2013/057891
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English (en)
Japanese (ja)
Inventor
小林　和人
侑助 中田
今村　公一
竜平 神崎
陽平 岡田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Bee Chemical Co Ltd
Teijin Ltd
Original Assignee
Nippon Bee Chemical Co Ltd
Teijin Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2012079768A external-priority patent/JP5925012B2/ja
Priority claimed from JP2012079755A external-priority patent/JP5925011B2/ja
Priority claimed from JP2012079756A external-priority patent/JP2013209482A/ja
Application filed by Nippon Bee Chemical Co Ltd, Teijin Ltd filed Critical Nippon Bee Chemical Co Ltd
Priority to US14/388,927 priority Critical patent/US9938426B2/en
Priority to CN201380028193.5A priority patent/CN104487524B/zh
Priority to KR1020147030463A priority patent/KR102066759B1/ko
Publication of WO2013146482A1 publication Critical patent/WO2013146482A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D147/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Coating compositions based on derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/36—Chemically modified polycondensates by etherifying
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C09D161/14—Modified phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/13338—Input devices, e.g. touch panels
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to a hard coating composition that provides a hard coat layer having high visibility and good hardness, and also has extensibility.
  • the present invention also provides a high refractive index antiblocking layer forming composition, an antiblocking film obtained by coating the high refractive index antiblocking layer forming composition, and a transparent conductive material on at least one surface of the antiblocking film.
  • the present invention relates to a transparent conductive laminate having a layer formed thereon.
  • Liquid crystal display devices have advantages such as thinness, light weight, and low power consumption, and are used in various fields such as computers, word processors, televisions, mobile phones, and portable information terminal devices.
  • touch panels having a mechanism for operating devices by holding down the display on the screen are rapidly spreading.
  • a touch panel has, for example, a mobile phone such as a smartphone, a tablet PC, a personal digital assistant device, a bank ATM, a vending machine, a personal digital assistant (PDA), a copying machine, a facsimile machine, and a game machine due to its excellent operability.
  • PDA personal digital assistant
  • a transparent conductive laminate having a transparent conductive layer provided on a transparent substrate is generally used.
  • ITO indium-tin oxide
  • a film such as a PET film or a polycarbonate film is often used from the viewpoint of high transparency and price.
  • These base films may be provided with a transparent hard coat layer for the purpose of improving scratch resistance and durability.
  • production of this interference fringe brings about the fall of visibility.
  • interference fringes depends on the refractive index difference between the transparent substrate film and the transparent hard coat layer and the extremely slight variation in the film thickness of the transparent hard coat layer.
  • the generation of such interference fringes is theoretically eliminated by completely eliminating variations in the film thickness of the transparent hard coat layer.
  • such means are unrealistic in the current technology and are extremely difficult to implement.
  • JP 2009-265590 A discloses a hard coating agent using fine particles of metal oxide such as zirconia, titanium oxide, ITO, ATO, ZnO, tin oxide, and zinc antimonate as a high refractive index agent. Describes a method of adjusting the refractive index of the hard coat layer by blending into the hard coat layer.
  • a high refractive index agent such as a metal oxide
  • Patent Document 2 describes a transparent hard coat layer-containing film having excellent visibility. And this patent document 2 has a reference about a high refractive index layer.
  • the high refractive index layer in Patent Document 2 is formed by vapor deposition or sputtering of a metal oxide such as ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 , ITO, or the like. It is formed by dispersing in a binder resin (such as [0007] paragraph).
  • Patent Document 3 describes a coating material that is formed in a layer on a transparent base body and has no noticeable interference fringes.
  • This coating material is characterized in that the attenuation coefficient is adjusted by blending fine particles and / or pigments.
  • various metals, metal oxides, metal nitrides, metal carbides are listed as fine particles, and azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, quinophthalone pigments are used as pigments. Pigments are mentioned (such as [0021] paragraph).
  • Patent Documents 1 to 3 disclose means for preventing generation of interference fringes and improving visibility. However, all of these Patent Documents 1 to 3 differ from the present invention in that a high refractive index agent such as a metal oxide is used.
  • Patent Document 4 describes an optical laminate in which the high refractive index hard coat layer contains a bromine-based resin (claim 1 and the like). This optical laminate is described as having improved optical characteristics, light resistance, hardware performance, and the like. On the other hand, the present invention does not use a brominated resin in increasing the refractive index of the hard coat layer, and the configuration of the invention is different from this invention.
  • Patent Document 5 JP-A-2008-239673
  • Patent Document 5 describes a transparent crosslinked film obtained by curing and crosslinking a vinyl ester composition, a polyfunctional acrylate and a composition containing a (meth) acrylate having a fluorene skeleton. (Claim 1).
  • This transparent crosslinked film is characterized by excellent surface hardness and no interference fringes.
  • the test is performed under the condition of a film thickness of 50 ⁇ m. This film thickness is very high compared with the film thickness generally used in the field of hard coat layers. Therefore, there is a cost disadvantage.
  • production suppression effect in the crosslinked film obtained by the composition described in this patent document 5 has not reached the level currently calculated
  • an object of the present invention is to provide a hard coating composition that forms a hard coat layer having high visibility and good hardness and also having extensibility.
  • the present invention can also provide a technique that can effectively prevent defects such as adhesion between layered materials such as a resin film, that is, a blocking phenomenon, without adversely affecting the visibility.
  • the present invention (A) A phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule
  • a hard coating composition comprising an acrylate compound, 60 to 85 parts by mass of phenol novolac acrylate (A) and 15 to 30 parts by mass of (meth) acrylate (B) with respect to 100 parts by mass of the resin component contained in the hard coating composition, A hard coating composition is provided, which solves the above problems.
  • the phenol novolac acrylate (A) is represented by the following formula (I)
  • R 1 is H or CH 2 OH
  • R 2 is H or OH
  • n is 2 to 5
  • m is 0 to 5.
  • the (meth) acrylate (B) is more preferably an aromatic group-containing (meth) acrylate having a refractive index in the range of 1.56 to 1.64.
  • the total content of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium-tin oxide is more preferably 0.0001% by mass or less in the composition.
  • the hard coat coating composition further comprises a component (C) a fluorene skeleton-containing (meth) acrylate having 2 or more (meth) acrylate groups, May include
  • the phenol novolac acrylate (A) is 40 to 70 parts by mass
  • the (meth) acrylate (B) is 10 to 30 parts by mass
  • the contained (meth) acrylate (C) is preferably contained in an amount of 15 to 40 parts by mass.
  • the fluorene skeleton-containing (meth) acrylate (C) is represented by the following formula (II)
  • each R 3 is independently H or CH 3 ;
  • A is independently, -OCH 2 CH 2 -, - OCH 2 CH 2 CH 2 -, - OCH (CH 3) CH 2 — Or —OCH 2 CH (CH 3 ) —, and each R is independently H or CH 3 .
  • the present invention also provides A transparent polymer substrate, and A hard coat layer formed by coating the hard coating composition on a substrate; A hard coat film having The hard coat layer has a refractive index of 1.565 to 1.620, A hard coat film is also provided.
  • the thickness of the hard coat layer is more preferably 0.05 to 10 ⁇ m.
  • the hard coat film is The substrate is a PET film having a thickness of 20 to 300 ⁇ m, More preferably, the hard coat film is characterized in that no crack is generated in the hard coat layer when the film is stretched 15% in the MD direction at 20 ° C. under the condition of a pulling speed of 5 mm / sec.
  • the hard coat film is
  • the base material is a polycarbonate film having a thickness of 30 to 200 ⁇ m, More preferably, the hard coat film is characterized in that cracks do not occur in any of the hard coat layer and the substrate when bent at 180 ° under the conditions of 25 ° C. and 60 degrees / second.
  • the present invention also provides a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of the hard coat film. More preferably, the transparent conductive layer is a crystalline layer containing indium oxide, and the thickness of the transparent conductive layer is 5 to 50 nm.
  • a metal oxide layer is present between the hard coat layer and the transparent conductive layer, and the thickness of the metal oxide layer is 0.5 to 5.0 nm.
  • the present invention also provides a touch panel having the transparent conductive laminate.
  • a high refractive index anti-blocking layer-forming composition comprising a first component and a second component,
  • the first component is an unsaturated double bond-containing acrylic copolymer
  • the second component is (A) A phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule Including acrylate,
  • the phenol novolac acrylate (A) is contained in an amount of 60 to 85 parts by mass and the (meth) acrylate (B) in an amount of 15 to 30 parts by mass with respect to 100 parts by mass of the second component.
  • the difference ⁇ SP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is in the range of 1 to 4,
  • the first component and the second component cause layer separation, and an antiblocking layer having fine irregularities on the surface is formed.
  • a high-refractive index anti-blocking layer forming composition is provided, which solves the above problems.
  • the phenol novolac acrylate (A) is represented by the following formula (I)
  • R 1 is H or CH 2 OH
  • R 2 is H or OH
  • n is 2 to 5
  • m is 0 to 5.
  • the (meth) acrylate (B) is preferably an aromatic group-containing (meth) acrylate having a refractive index in the range of 1.56 to 1.64.
  • the total content of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium-tin oxide is 0.0001% by mass or less in the composition. preferable.
  • the present invention also provides A transparent polymer substrate, and An anti-blocking layer formed by coating the substrate with the high refractive index anti-blocking layer forming composition, An anti-blocking film having The anti-blocking layer has a refractive index of 1.565 to 1.620, and The anti-blocking layer has an arithmetic average roughness (Ra) of 0.001 to 0.09 ⁇ m and a ten-point average roughness (Rz) of 0.01 to 0.5 ⁇ m.
  • Ra arithmetic average roughness
  • Rz ten-point average roughness
  • the thickness of the anti-blocking layer is preferably 0.05 to 10 ⁇ m.
  • the substrate is a PET film having a thickness of 20 to 300 ⁇ m
  • Examples of the anti-blocking film include those characterized in that no cracks are generated in the anti-blocking layer when the film is stretched 15% in the MD direction at 20 ° C. under a pulling speed of 5 m / min.
  • the base material is a polycarbonate film having a thickness of 30 to 200 ⁇ m
  • Examples of the anti-blocking film include those characterized in that cracks do not occur in either the anti-blocking layer or the substrate when bent 180 ° under the conditions of 25 ° C. and 60 degrees / second.
  • the anti-blocking film preferably has a total light transmittance of 88% or more and a haze value of 2% or less.
  • the present invention further provides a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface of the anti-blocking film.
  • the transparent conductive layer is a crystalline layer containing indium oxide and the thickness of the transparent conductive layer is 5 to 50 nm.
  • a metal oxide layer exists between the anti-blocking layer and the transparent conductive layer, and the thickness of the metal oxide layer is 0.5 to 5.0 nm.
  • the present invention also provides a touch panel having the transparent conductive laminate.
  • the hard coating composition of the present invention provides a transparent hard coat layer provided on a transparent polymer substrate.
  • the transparent hard coat layer formed by the hard coating composition of the present invention is characterized by having good hardness and high visibility and extensibility.
  • the transparent hard coat layer formed by the hard coating composition of the present invention has a high refractive index. Therefore, even when the transparent hard coat layer in the present invention is provided on a base film having a high refractive index such as a PET film or a polycarbonate film, there is an advantage that no interference fringes are generated.
  • the hard coating composition of the present invention is further characterized by having a high refractive index even without containing a high refractive index agent such as a metal oxide. Therefore, the obtained transparent hard coat layer is characterized by having high extensibility in addition to high hardness and refractive index.
  • a fluorene skeleton-containing (meth) acrylate having two or more (meth) acrylate groups is blended as the component (C). You can also. When the component (C) is blended, the refractive index can be set higher.
  • the hard coating composition of the present invention even when a transparent hard coat layer is formed on a base film having a high refractive index such as a PET film or a polycarbonate film, it has high visibility and good hardness. In addition, there is an advantage that a hard coat layer having extensibility is provided.
  • the anti-blocking layer-forming composition of the present invention can provide an anti-blocking layer that is a resin layer having irregularities on the surface, simply by photocuring after coating on a substrate and drying as necessary. .
  • the obtained anti-blocking film has high hardness and is hardly damaged.
  • no particulate matter having an average particle diameter of more than 0.5 ⁇ m is used, there is an advantage that visibility and optical characteristics are not impaired.
  • the anti-blocking film obtained by coating the anti-blocking layer forming composition of the present invention exhibits an effect that a blocking phenomenon (for example, interlayer adhesion) does not occur even when a plurality of the anti-blocking films are overlapped.
  • a blocking phenomenon for example, difficulty of peeling from a winding roll
  • the obtained anti-blocking layer has a high refractive index and also has excellent extensibility. Due to this feature, the occurrence of interference fringes can be suppressed, and there is an advantage that extremely high visibility is achieved.
  • 4 is a graph showing a transmission spectrum (transmittance (%)) in a wavelength range of 400 to 800 nm of a hard coat layer obtained using the hard coating composition of Example E1.
  • 6 is a graph showing a transmission spectrum (transmittance (%)) in a wavelength range of 400 to 800 nm of a hard coat layer obtained using the hard coating composition of Comparative Example E10.
  • 4 is a graph showing a transmission spectrum (transmittance (%)) in a wavelength range of 400 to 800 nm of a hard coat layer obtained using the hard coating composition of Example F1.
  • the hard coating composition of the present invention comprises: (A) A phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule Contains acrylate compounds.
  • the phenol novolac acrylate (A) is contained in an amount of 40 to 90 parts by mass and the (meth) acrylate (B) is contained in an amount of 10 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition.
  • the hard coating composition of the present invention comprises (A) a phenol novolac acrylate having 2 or more acrylate groups.
  • the hard coating composition contains the phenol novolac acrylate (A)
  • the resulting hard coat layer becomes a high refractive index layer that is transparent and has high hardness. Thereby, generation
  • Phenol novolac acrylate (A) is represented by the following formula (I)
  • R 1 is H or CH 2 OH
  • R 2 is H or OH
  • n is 2 to 5
  • m is 0 to 5.
  • n is preferably 2 to 4
  • m is preferably 0 to 3
  • more preferably n is 2 to 4
  • m is more preferably 0 to 1.
  • the weight average molecular weight of the phenol novolac acrylate (A) is preferably 400 to 2500, more preferably 450 to 2000.
  • the hydroxyl value of the phenol novolak acrylate (A) is preferably 100 to 180 mgKOH / g, more preferably 120 to 160 mgKOH / g.
  • the weight average molecular weight of each component can be measured by a gel permeation chromatography method.
  • a high-speed GPC device such as HLC-8220 GPC (manufactured by Tosoh Corporation) can be used.
  • HLC-8220GPC manufactured by Tosoh Corporation
  • 2 g of a test sample was weighed and treated in a vacuum dryer at 40 ° C. for 2 hours to remove moisture, and then a THF solution. And a measurement is performed under the conditions of a column injection amount: 10 ⁇ l and a flow rate: 0.35 ml / min.
  • the phenol novolac acrylate (A) is provided on the condition that it is contained in an amount of 60 to 85 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition.
  • the amount of the phenol novolac acrylate (A) is less than 60 parts by mass and when the amount of the phenol novolac acrylate (A) exceeds 85 parts by mass, the hardness of the resulting hard coat layer is low. There is a bug.
  • (B) Aromatic group-containing mono- or poly (meth) acrylate compound having 1 to 2 mol of alkylene oxide structure of 2 or 3 carbon atoms in the molecule.
  • the hard coating composition of the present invention comprises (B) 2 or 3 carbon atoms. And an aromatic group-containing mono- or poly (meth) acrylate having 1 to 2 mol of an alkylene oxide structure in the molecule.
  • the (meth) acrylate (B) preferably has a viscosity of less than 300 mPa ⁇ s and a refractive index in the range of 1.56 to 1.64.
  • the viscosity of component (B) it is possible to design the viscosity of component (B) to be less than 300 mPa ⁇ s by including 1-2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule. Become. Further, in the (meth) acrylate of the component (B), when the alkylene oxide structure having 2 or 3 carbon atoms is contained in the molecule in an amount of 1 to 2 mol, the extensibility of the obtained hard coat layer is improved.
  • examples of the “alkylene structure having 2 or 3 carbon atoms” include an ethylene oxide structure and a propylene oxide structure.
  • Component (B) (meth) acrylate is further characterized by having an aromatic group.
  • a high refractive index such as a refractive index in the range of 1.56 to 1.64 is achieved.
  • Examples of the aromatic group-containing (meth) acrylate that can be preferably used as the component (B) in the present invention include, for example, an alkyleneoxylated phenol (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule.
  • Examples include acrylate, alkyleneoxylated orthophenylphenol (meth) acrylate, alkyleneoxylated metaphenylphenol (meth) acrylate, alkyleneoxylated paraphenylphenol (meth) acrylate, and alkyleneoxylated cumylphenol (meth) acrylate.
  • (meth) acrylate having two aromatic groups is more preferable in that it has a high refractive index.
  • the refractive index of component (B) can be measured with an Abbe refractometer by a method based on JIS K0062.
  • the viscosity of the component (B) is preferably less than 300 mPa ⁇ s.
  • the viscosity of component (B) is more preferably in the range of 1 to 300 mPa ⁇ s, still more preferably in the range of 1 to 200 mPa ⁇ s.
  • the viscosity of component (B) can be measured with a B-type viscometer (TVB-22L, manufactured by Toki Sangyo Co., Ltd.).
  • B-type viscometer examples include TVB-22L (manufactured by Toki Sangyo Co., Ltd.).
  • Component (B) preferably has a weight average molecular weight in the range of 150 to 600, and more preferably in the range of 200 to 400.
  • the component (B) is contained in an amount of 15 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition.
  • the (meth) acrylate (B) is contained in the hard coating composition in the above mass range, there is an advantage that the obtained hard coat layer has high hardness and high refractive index.
  • the amount of the component (B) is less than 15 parts by mass and when the amount of the component (B) exceeds 30 parts by mass, there is a problem that the hardness of the obtained hard coat layer is lowered.
  • (C) A fluorene skeleton-containing (meth) acrylate having two or more (meth) acrylate groups
  • skeleton containing (meth) acrylate (C) which has the (meth) acrylate group beyond it is mentioned. Since the fluorene skeleton-containing (meth) acrylate (C) has a high refractive index, there is an advantage that the refractive index of the obtained hard coat layer can be set high.
  • each R 3 is independently H or CH 3 ;
  • A is independently, -OCH 2 CH 2 -, - OCH 2 CH 2 CH 2 -, - OCH (CH 3) CH 2 — Or —OCH 2 CH (CH 3 ) —, and each R is independently H or CH 3 .
  • a more preferred example of the fluorene skeleton-containing (meth) acrylate (C) is an acrylate monomer represented by the following formula (II) -1.
  • (II) -1 [In the above formula (II) -1, each R represents a hydrogen atom or a methyl group, and m and n each independently represents an integer of 1 to 5. ]
  • fluorene skeleton-containing (meth) acrylate (C) a commercially available product may be used.
  • the commercially available fluorene skeleton-containing (meth) acrylate (C) include the NK ester series marketed by Shin-Nakamura Chemical Co., Ltd. and the Ogsol EA series marketed by Osaka Gas Chemical Co., Ltd.
  • the phenol novolac acrylate (A) is 40 to 70 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition.
  • Parts, (meth) acrylate (B) is contained in an amount of 10 to 30 parts by mass
  • fluorene skeleton-containing (meth) acrylate (C) is contained in an amount of 15 to 40 parts by mass.
  • the phenol novolac acrylate (A) is 40 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition. It is necessary to contain ⁇ 70 parts by mass.
  • the amount of the phenol novolac acrylate (A) is less than 40 parts by mass and when the amount of the phenol novolac acrylate (A) exceeds 70 parts by mass, the hardness of the obtained hard coat layer is low. There is a bug.
  • the (meth) acrylate of the component (B) is based on 100 parts by mass of the resin component contained in the hard coating composition. It is necessary to contain 10 to 30 parts by mass.
  • the (meth) acrylate (B) is contained in the hard coating composition in the above mass range, there is an advantage that the obtained hard coat layer has high hardness and high refractive index.
  • the amount of the component (B) is less than 10 parts by mass and when the amount of the component (B) exceeds 30 parts by mass, there is a problem that the hardness of the obtained hard coat layer is lowered.
  • the component (C) When the fluorene skeleton-containing (meth) acrylate of the component (C) is contained in the hard coat coating composition, the component (C) is contained in 15 to 40 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition. On condition that When the amount of the component (C) exceeds 40 parts by mass, the hardness of the obtained hard coat layer may be lowered.
  • the hard coating composition of the present invention may contain other (meth) acrylates in addition to the components (A) and (B) and, if necessary, the component (C).
  • examples of such (meth) acrylates include polyfunctional (meth) acrylate monomers and / or oligomer compounds. These polyfunctional (meth) acrylate monomers and / or oligomer compounds have a high hardness due to a curing reaction based on the reaction of (meth) acryloyl groups by irradiation with active energy rays after the hard coating composition is applied. There is an advantage that a hard coat layer can be obtained.
  • the polyfunctional (meth) acrylate monomer and / or oligomer compound preferably has three or more (meth) acryloyl groups.
  • three or more (meth) acryloyl groups there is an advantage that a hard coat layer having high hardness can be obtained after irradiation with active energy rays.
  • polyfunctional (meth) acrylate monomer and / or oligomer compound include, for example, hydroxypropylated trimethylolpropane triacrylate, isocyanuric acid ethylene oxide modified diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and trimethylolpropane triacrylate.
  • examples thereof include acrylate, tris (acryloxyethyl) isocyanurate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and oligomers thereof. These monomers or oligomers may be used alone or in combination of two or more.
  • the hard coating composition contains other (meth) acrylates, it is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the hard coating composition. More preferably, it is in the range of parts by mass.
  • the hard coating composition of the present invention such as a photopolymerization initiator preferably contains a photopolymerization initiator. Due to the presence of the photopolymerization initiator, the resin component is favorably polymerized by irradiation with active energy rays such as ultraviolet rays.
  • photopolymerization initiators include alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and oxime ester polymerization initiators.
  • alkylphenone photopolymerization initiators examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane.
  • acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.
  • titanocene photopolymerization initiators include bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium Is mentioned.
  • Examples of the oxime ester polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, 2- (2-hydroxy And ethoxy) ethyl ester.
  • These photoinitiators may be used individually by 1 type, and may use 2 or more types together.
  • a preferable amount of the photopolymerization initiator is 100 parts by mass of the above components (A) and (B), and if necessary, the component (C) and other (meth) acrylates (these are collectively referred to as “resin component”).
  • the amount is 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass.
  • the hard coating composition used in the present invention may contain a solvent.
  • the solvent is not particularly limited, and can be appropriately selected in consideration of the components contained in the composition, the type of base material to be coated, the coating method of the composition, and the like.
  • Specific examples of the solvent that can be used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, and ethylene glycol.
  • Ether solvents such as dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole and phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate and ethylene glycol diacetate; dimethylformamide, Amide solvents such as diethylformamide and N-methylpyrrolidone; methyl Cellosolve, ethyl cellosolve, cellosolve solvents such as butyl cellosolve; methanol, ethanol, alcohol solvents such as propanol; and the like; dichloromethane, halogenated solvents such as chloroform. These solvents may be used alone or in combination of two or more. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.
  • the hard coating composition of the present invention can contain various additives as required.
  • additives include conventional additives such as antistatic agents, plasticizers, surfactants, and antioxidants.
  • the hard coating composition of the present invention does not need to contain a high refractive index agent composed of a metal oxide such as ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 or indium-tin oxide due to the above configuration. It is characterized in that a hard coat layer having a high refractive index can be formed. Therefore, the hard coating composition of the present invention does not contain a high refractive index agent such as a metal oxide selected from the group consisting of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium-tin oxide. Is preferred.
  • the hard coating composition preferably has a total content of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium-tin oxide of 0.0001% by mass or less in the composition. . This is because when a high refractive index agent such as a metal oxide is present in the hard coat layer, the stretchability and the bending resistance are generally inferior as compared with the layer containing only the resin component.
  • the present invention further provides a hard coat film formed using the above hard coating composition.
  • This hard coat film has a transparent polymer base material and a hard coat layer formed by coating the base material with the hard coating composition.
  • the hard coat layer in the present invention is characterized by having a high refractive index of 1.565 to 1.620.
  • a PET film or a polycarbonate film is preferably used as the transparent polymer substrate.
  • the PET film and the polycarbonate film are suitably used as a base film for a film having a transparent conductive layer constituting a touch panel from the viewpoints of high film strength and transparency and low cost.
  • these films generally have a high refractive index of 1.5 or more. Since the refractive index of these films is higher than the refractive index of the resin component constituting the normally used hard coat film, the difference in refractive index with the hard coat layer increases, and the frequency of occurrence of interference fringes increases. There's a problem.
  • the interference fringes refer to iris-like reflection caused by interference of light reflected at each interface in a multilayer body composed of a transparent film and a transparent coat layer. This interference fringe tends to appear prominently under irradiation of a three-wavelength fluorescent lamp.
  • the three-wavelength light-emitting fluorescent lamp is a fluorescent lamp characterized by a strong emission intensity at a specific wavelength, which is characterized by the fact that things can be clearly seen.
  • the hard coating composition of the present invention is characterized in that a hard coat layer having a high refractive index can be formed. Therefore, even if a transparent hard coat layer is formed on a transparent substrate film such as a PET film or a polycarbonate film, there is a feature that no interference fringes are generated.
  • the hard coating composition of the present invention may be applied to a base film other than the PET film or the polycarbonate film.
  • a base film include triacetyl cellulose (TAC) film, diacetylene cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, polyester film, and polysulfone.
  • TAC triacetyl cellulose
  • diacetylene cellulose film acetate butyrate cellulose film
  • polyether sulfone film polyacrylic resin film, polyurethane resin film, polyester film, and polysulfone.
  • examples thereof include a film, a polyether film, a polymethylpentene film, a polyether ketone film, and a (meth) acrylonitrile film.
  • the thickness of the transparent polymer substrate can be appropriately selected according to the use, but is generally about 20 to 300 ⁇ m.
  • the hard coat layer is formed by applying the above hard coating composition on a transparent polymer substrate.
  • the coating method of the hard coating composition can be selected as appropriate according to the situation of the hard coating composition and the painting process. For example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method It can be applied by a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294).
  • the thickness of the hard coat layer is not particularly limited and can be set in a timely manner in consideration of various factors.
  • the hard coating composition can be applied so as to obtain a hard coat layer of 0.01 to 20 ⁇ m.
  • a hard coat layer is formed by curing the coating film obtained by applying the coating composition.
  • This curing can be performed by irradiation using a light source that emits an active energy ray having a wavelength as required.
  • a light source that emits an active energy ray having a wavelength as required.
  • the active energy ray to be irradiated for example, light having an exposure dose of 0.1 to 1.5 J / cm 2 , preferably 0.3 to 1.5 J / cm 2 can be used.
  • the wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like.
  • the hard coat film of the present invention is characterized in that a high refractive index of 1.565 to 1.620 of the hard coat layer is achieved without using a high refractive index agent.
  • the refractive index of the hard coat layer can be measured in accordance with JIS K7142 using, for example, an Abbe refractometer.
  • the hard coat film of the present invention preferably has a total light transmittance of 85% or more, more preferably 90% or more. Further, the hard coat film of the present invention preferably has a haze of 2% or less, more preferably 1% or less.
  • ZnO since the TiO 2, CeO 2, SnO 2 , be free of high refractive index such as ZrO 2 high refractive index has been achieved, need to include such a high refractive index agent There is no. Therefore, it is possible to achieve a high total light transmittance and a low haze value as described above.
  • the total light transmittance (T t (%)) is calculated by the following equation by measuring the incident light intensity (T 0 ) with respect to the hard coat film and the total transmitted light intensity (T 1 ) transmitted through the hard coat film. .
  • the haze is calculated from the following formula in accordance with JIS K7105.
  • H Haze (cloudiness value) (%)
  • T d Diffuse transmittance (%)
  • T t Total light transmittance (%)
  • the total light transmittance and the haze value can be measured using, for example, a haze meter (manufactured by Suga Test Instruments Co., Ltd.).
  • the hard coat layer formed using the hard coating composition of the present invention is characterized by having high extensibility in addition to high hardness and refractive index. Therefore, the hard coat film in this invention can be used suitably in preparation of the film which has a transparent conductive layer which comprises a touchscreen etc., for example.
  • a transparent conductive layer and an optical interference layer for controlling the reflectance by optical interference can be used in combination in an appropriate order as required.
  • the order in which the transparent conductive layer, the optical interference layer, and the hard coat layer are laminated is not particularly limited as long as the function expected to be exhibited is achieved according to the application.
  • the transparent conductive layer is A
  • the optical interference layer is B
  • the hard coat layer that is the subject of the present invention is C
  • the transparent polymer substrate is D
  • the subject is not subject to the present invention.
  • a / B / C / D / E, A / B / C / D / C, A / B / B / C / D / E, A / B / B / C / D / C, A / C / D / E / B, A / C / D / C / B, A / C / D / E / B, A / C / D / C / B, A / C / D / E / B / B, A / C / D / C / B / B, etc. can do.
  • the optical interference layer described above refers to a layer that prevents or suppresses reflected light by appropriately combining a high refractive index layer and a low refractive index layer.
  • the optical interference layer is composed of at least one high refractive index layer and at least one low refractive index layer. Two or more combination units of the high refractive index layer and the low refractive index layer may be used.
  • the thickness of the optical interference layer is preferably 30 nm to 150 nm, and more preferably 50 nm to 150 nm.
  • the optical interference layer can be formed by either a wet method or a dry method.
  • a wet method such as a doctor knife, bar coater, gravure roll coater, curtain coater, knife coater, spin coater, etc., spray method, dipping method, etc., dry method such as PVD method such as sputtering method, vacuum deposition method, ion plating method, etc. Printing method, CVD method, etc. can be applied.
  • a transparent conductive laminate constituting a touch panel or the like is generally a film having a transparent conductive layer.
  • the transparent conductive layer is not particularly limited, but is a crystalline layer containing indium oxide, more specifically indium such as ITO (indium-tin oxide) and IZO (indium-zinc oxide).
  • ITO indium-tin oxide
  • IZO indium-zinc oxide
  • a crystalline layer is preferably used.
  • a method for forming the transparent conductive layer there are a PVD method such as a sputtering method, a vacuum deposition method, and an ion plating method, a coating method, a printing method, and a CVD method, and the PVD method or the CVD method is preferable.
  • the hard coat layer provided using the hard coating composition of the present invention is characterized by having high visibility and good hardness and high extensibility. Due to the high extensibility of the obtained hard coat layer, even when the base film is locally thermally expanded by heating in the stage of providing the transparent conductive layer, the hard coat layer follows well, As a result, there is an advantage that defects such as film warp do not occur.
  • the transparent polymer substrate on which the hard coating composition is applied is a hard coat film having a thickness of 20 to 300 ⁇ m
  • this hard coat film When the film is stretched by 15% in the MD direction at 20 ° C. under the condition of a pulling speed of 5 mm / sec, there is a state in which no crack is generated in the hard coat layer.
  • the thickness of the hard coat layer is, for example, 0.05 to 10 ⁇ m.
  • the production of a polymer base film is performed by winding a resin base material in a molten state in a roll shape while being perpendicular to the vertical direction (winding direction: MD direction) and the horizontal direction (TD direction: MD direction).
  • the film is produced by a biaxial stretching method in which a film having a uniform thickness is produced.
  • high stress remains in the MD direction. Therefore, the obtained film tends to cause thermal expansion / shrinkage particularly in the MD direction.
  • Generation of cracks (film cracks) and the like can be effectively verified by performing a test in which the obtained hard coat film is stretched in the MD direction, which is the direction wound during the production of the polymer base film. There is an advantage.
  • the transparent polymer substrate constituting the hard coat film is a polycarbonate film
  • the elongation performance of the formed hard coat layer can be evaluated by verifying the bending resistance of the hard coat film.
  • Polycarbonate is a material with excellent physical properties such as heat resistance and impact resistance, but especially in the case of a polycarbonate film with a thin film thickness, cracks may occur due to stress such as bending.
  • a polycarbonate film having a thin film thickness is used as a base film, when the hard coat layer formed on the base film has high extensibility, by providing the hard coat layer, It becomes possible to prevent the occurrence of cracks.
  • the hard coat layer formed by the hard coating composition of the present invention has high extensibility.
  • the hard coat film using a polycarbonate having a thin film thickness as a base film there is an advantage that toughness against bending stress can be improved. More specifically, when the transparent polymer substrate to which the hard coating composition is applied is a hard coat film which is a polycarbonate film having a thickness of 30 to 200 ⁇ m, the hard coat film is treated at 25 ° C. and 60 degrees / degree. Even when it is bent 180 ° under the second condition, there is a state in which no crack occurs in either the hard coat layer or the substrate.
  • the thickness of the hard coat layer may be 0.05 to 10 ⁇ m.
  • the hard coat layer formed using the hard coating composition of the present invention is characterized by having good hardness and high visibility and extensibility.
  • the transparent hard coat layer formed by the hard coating composition of the present invention has a high refractive index. Therefore, even when the transparent hard coat layer in the present invention is provided on a base film having a high refractive index such as a PET film or a polycarbonate film, there is an advantage that no interference fringes are generated.
  • the hard coat layer in the present invention can be suitably used in a film having a transparent conductive layer constituting a touch panel electrode.
  • the high refractive index antiblocking layer forming composition of the present invention comprises a first component and a second component.
  • the first component is an unsaturated double bond-containing acrylic copolymer.
  • the second component includes (A) a phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule.
  • the phenol novolac acrylate (A) is contained in an amount of 60 to 85 parts by mass and the (meth) acrylate (B) in an amount of 15 to 30 parts by mass with respect to 100 parts by mass of the second component.
  • the difference ⁇ SP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is in the range of 1 to 4, and the first component and the second component contained in the composition
  • This high refractive index anti-blocking layer forming composition is characterized in that after coating, the first component and the second component cause layer separation, and an anti-blocking layer having fine irregularities on the surface is formed.
  • an unsaturated double bond-containing acrylic copolymer is used as the first component.
  • An unsaturated double bond-containing acrylic copolymer is, for example, a resin obtained by copolymerizing a (meth) acrylic monomer and another monomer having an ethylenically unsaturated double bond, a (meth) acrylic monomer and another ethylenically unsaturated Acrylic acid or glycidyl acrylate for resins reacted with monomers having double bonds and epoxy groups, resins made by reacting (meth) acrylic monomers with other monomers having ethylenically unsaturated double bonds and isocyanate groups, etc. And those having an unsaturated double bond and other functional groups added thereto.
  • the unsaturated double bond-containing acrylic copolymers may be used alone, or two or more thereof may be mixed and used.
  • the unsaturated double bond-containing acrylic copolymer preferably has a weight average molecular weight of 2,000 to 100,000, more preferably 5,000 to 50,000.
  • the second component is: (A) A phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule Acrylate, including.
  • a phenol novolak acrylate having 2 or more acrylate groups and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule Acrylate, including.
  • the phenol novolac acrylate (A) is provided on the condition that it is contained in an amount of 60 to 85 parts by mass with respect to 100 parts by mass of the second component.
  • the amount of the phenol novolac acrylate (A) is less than 60 parts by mass and when the amount of the phenol novolac acrylate (A) exceeds 85 parts by mass, the hardness of the obtained anti-blocking layer is low. There is a bug.
  • (B) Aromatic group-containing mono- or poly (meth) acrylate compound having 1 to 2 mol of alkylene oxide structure of 2 or 3 carbon atoms in the molecule.
  • This component (B) is a component of component (B) of the hard coat coating composition. The description is omitted because it is an aromatic group-containing mono- or poly (meth) acrylate compound having the same alkylene oxide structure having 2 or 3 carbon atoms in the molecule and having 1 to 2 mol in the molecule.
  • the component (B) is included in an amount of 15 to 30 parts by mass with respect to 100 parts by mass of the second component contained in the high refractive index antiblocking layer forming composition.
  • the obtained anti-blocking layer has an advantage of high hardness and high refractive index.
  • the amount of the component (B) is less than 15 parts by mass and when the amount of the component (B) exceeds 30 parts by mass, there is a problem that the hardness of the obtained anti-blocking layer is lowered.
  • the second component in the high refractive index anti-blocking layer forming composition of the present invention may contain other (meth) acrylates in addition to the components (A) and (B). Omitted Such (meth) acrylates are the same as "other (meth) acrylates" according to the hard coating composition.
  • the second component contained in the high-refractive index anti-blocking layer forming composition contains other (meth) acrylates
  • 100 parts by mass of the second component contained in the high-refractive index anti-blocking layer forming composition The range is preferably 1 to 30 parts by mass, and more preferably 1 to 25 parts by mass.
  • High refractive index antiblocking layer forming composition is composed of a first component and a second component, and addition of a solvent, a photopolymerization initiator, a catalyst, a photosensitizer and the like as required. It is prepared by mixing the agent.
  • phase separation is caused by the difference in SP value between the first component and the second component.
  • the difference ( ⁇ SP) between the SP value of the first component and the SP value of the second component is within the range of 1 to 4.
  • the compatibility of the resins with each other is low, whereby the first component and the second component are applied after application of the anti-blocking layer forming composition. It is thought that phase separation is brought about.
  • the ⁇ SP is more preferably in the range of 2.0 to 3.5.
  • the SP value is an abbreviation for solubility parameter (solubility parameter) and is a measure of solubility.
  • solubility parameter is a measure of solubility.
  • the SP value indicates that the polarity is higher as the numerical value is larger, and the polarity is lower as the numerical value is smaller.
  • the SP value can be measured by the following method [References: SUH, CLARKE, J. et al. P. S. A-1, 5, 1671-1681 (1967)].
  • Measurement temperature 20 ° C
  • Sample Weigh 0.5 g of resin in a 100 ml beaker, add 10 ml of good solvent using a whole pipette, and dissolve with a magnetic stirrer.
  • solvent Good solvent: Dioxane, acetone, etc. Poor solvent: n-hexane, ion-exchanged water, etc.
  • Muddy point measurement The poor solvent is added dropwise using a 50 ml burette, and the point at which turbidity occurs is defined as the amount of addition.
  • the SP value ⁇ of the resin is given by the following equation.
  • the high refractive index antiblocking layer-forming composition of the present invention may further contain components such as various solvents, photopolymerization initiators and additives in addition to the first component and the second component.
  • Preferred organic solvents when the first component and the second component are the above combinations include, for example, ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol
  • An ether solvent such as anisole, phenetol propylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether;
  • One of these solvents may be used alone, or two or more organic solvents may be mixed and used.
  • a solvent for example, 1 to 9900 parts by mass, preferably 10 to 900 parts by mass are added to 100 parts by mass of the total amount of the first component and the second component (collectively referred to as “resin component”). Can do.
  • the high refractive index anti-blocking layer forming composition preferably contains a photopolymerization initiator.
  • the photopolymerization initiator include 2-hydroxy-2methyl-1phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc. Can be mentioned.
  • a preferable amount of the photopolymerization initiator is 0.01 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin component.
  • the high refractive index anti-blocking layer forming composition may contain conventional additives such as an antistatic agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, if necessary.
  • additives such as an antistatic agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, if necessary.
  • the amount is preferably 0.01 to 20 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the resin component.
  • the high refractive index anti-blocking layer forming composition can form a resin layer having irregularities without using resin particles or the like by using the first component and the second component as described above. There is. Therefore, it is preferable that the anti-blocking layer forming composition does not contain resin particles.
  • the anti-blocking layer forming composition may contain at least one or more inorganic particles, organic particles, or a composite thereof, if necessary. These particles are not particularly added for the purpose of forming irregularities on the surface, but are added to form more uniform and fine irregularities by controlling phase separation and precipitation. These particles have an average particle size of 0.5 ⁇ m or less, preferably 0.01 to 0.3 ⁇ m. When it exceeds 0.5 ⁇ m, the transparency slightly decreases.
  • inorganic particles include silica, alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / tin oxide), ATO There may be mentioned at least one selected from the group consisting of (antimony oxide / tin oxide), tin oxide, indium oxide and antimony oxide.
  • organic particles include at least one selected from the group consisting of acrylic, olefin, polyether, polyester, urethane, polyester, silicone, polysilane, polyimide, and fluorine particles.
  • the anti-blocking layer having fine irregularities on the surface can be formed by coating the high refractive index anti-blocking layer forming composition and then curing the composition.
  • the coating method of the anti-blocking layer forming composition include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and extrusion coating.
  • the thickness of the anti-blocking layer include an embodiment having a thickness of 0.01 to 20 ⁇ m.
  • the high refractive index antiblocking layer-forming composition After coating the high refractive index antiblocking layer-forming composition, it can be phase separated and cured by irradiating light.
  • the light to be irradiated for example, light having an exposure amount of 0.1 to 3.5 J / cm 2 , preferably 0.5 to 1.5 J / cm 2 can be used.
  • the wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like. By irradiating light in this way, phase separation and curing will occur.
  • Anti-blocking film This invention further provides the anti-blocking film formed using the said high refractive index anti-blocking layer forming composition.
  • This anti-blocking film has a transparent polymer base material and an anti-blocking layer formed by coating the high refractive index anti-blocking layer forming composition on the base material.
  • the anti-blocking layer in the present invention is characterized by having a high refractive index of 1.565 to 1.620 in addition to having an excellent anti-blocking performance.
  • a PET film or a polycarbonate film is preferably used as the transparent polymer substrate.
  • the PET film and the polycarbonate film are suitably used as a base film for a film having a transparent conductive layer constituting a touch panel from the viewpoints of high film strength and transparency and low cost.
  • these films generally have a high refractive index of 1.5 or more. Since the refractive index of these films is higher than the refractive index of the resin component constituting the commonly used anti-blocking film, the difference in refractive index with the anti-blocking layer increases, and the frequency of occurrence of interference fringes increases. There's a problem.
  • the interference fringes refer to iris-like reflection caused by interference of light reflected at each interface in a multilayer body composed of a transparent film and a transparent coat layer. This interference fringe tends to appear prominently under irradiation of a three-wavelength fluorescent lamp.
  • the three-wavelength light-emitting fluorescent lamp is a fluorescent lamp characterized by a strong emission intensity at a specific wavelength, which is characterized by the fact that things can be clearly seen.
  • the high refractive index anti-blocking layer forming composition of the present invention is characterized in that an anti-blocking layer having a high refractive index can be formed. Therefore, even if an antiblocking layer is formed on a transparent substrate film such as a PET film or a polycarbonate film, there is a feature that no interference fringes are generated.
  • the high refractive index anti-blocking layer forming composition of the present invention may be applied to a substrate film other than the PET film or the polycarbonate film.
  • a base film include triacetyl cellulose (TAC) film, diacetylene cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, polyester film, and polysulfone.
  • TAC triacetyl cellulose
  • diacetylene cellulose film acetate butyrate cellulose film
  • polyether sulfone film polyacrylic resin film
  • polyurethane resin film polyester film
  • polysulfone examples thereof include a film, a polyether film, a polymethylpentene film, a polyether ketone film, and a (meth) acrylonitrile film.
  • the thickness of the transparent polymer substrate can be appropriately selected according to the use, but is generally about 20 to 300 ⁇ m.
  • the anti-blocking layer formed by the high refractive index anti-blocking layer forming composition of the present invention has fine irregularities.
  • the arithmetic average roughness (Ra) of the surface roughness curve of the anti-blocking layer is preferably less than 0.1 ⁇ m, more preferably 0.001 to 0.09 ⁇ m, and 0.002 to 0.00. Particularly preferred is 08 ⁇ m.
  • the arithmetic average roughness (Ra) of the roughness curve is a parameter defined in JIS B 0601-2001.
  • the arithmetic average roughness (Ra) of the surface roughness curve of the anti-blocking layer is 0.1 ⁇ m or more, problems such as generation of glare and whitening of the coating film may occur. If the value of Ra is less than the particularly preferable range, a blocking phenomenon occurs, which is not preferable.
  • JIS B 0601-2001 is a Japanese industrial standard and is a standard based on ISO 4288.
  • Arithmetic average roughness (Ra) of the roughness curve is a sample of only the reference length in the direction of the average line from the roughness curve, the X axis in the direction of the average line of this extracted portion, and Y in the direction of the vertical magnification.
  • y f (x)
  • ⁇ m micrometers
  • the anti-blocking layer formed by the high refractive index anti-blocking layer forming composition of the present invention preferably has an Rz of 0.5 ⁇ m or less.
  • Rz is the ten-point average roughness of the roughness curve, and is a parameter defined in JIS B0601-2001.
  • Rz is more preferably 0.3 ⁇ m or less, and further preferably 0.2 ⁇ m or less.
  • the lower limit is preferably 0.01 ⁇ m.
  • the arithmetic average roughness (Ra) and ten-point average roughness (Rz) of the surface roughness curve of the anti-blocking layer formed by the high refractive index anti-blocking layer forming composition of the present invention are, for example, manufactured by Kosaka Laboratory Ltd. Can be measured according to JIS B 0601-2001 using a high-precision fine shape measuring instrument or a color 3D laser microscope manufactured by Keyence Corporation.
  • the anti-blocking layer formed by the high-refractive index anti-blocking layer forming composition of the present invention has an irregular, fine and dense uneven shape, and therefore exhibits excellent anti-blocking properties.
  • the anti-blocking layer in the present invention is also advantageous in that the sharpness of an image displayed by a light source such as a liquid crystal module is not deteriorated.
  • the pitch of light rays emitted from the liquid crystal has become finer. Therefore, in order to maintain image clarity, a finer and denser uneven shape is required.
  • the anti-blocking layer in the present invention has an advantage that it has a fine and dense concavo-convex shape and is not accompanied by a decrease in image sharpness such as a decrease in contrast and a decrease in luminance.
  • the anti-blocking layer in the present invention is characterized in that the refractive index of the anti-blocking layer is as high as 1.565 to 1.620 without using a high refractive index agent.
  • the refractive index of the anti-blocking layer can be measured using an Abbe refractometer according to JIS K7142.
  • the anti-blocking film of the present invention preferably has a total light transmittance of 85% or more, and more preferably 90% or more. Further, the anti-blocking film of the present invention preferably has a haze of 2% or less, more preferably 1% or less.
  • ZnO since the TiO 2, CeO 2, SnO 2 , be free of high refractive index such as ZrO 2 high refractive index has been achieved, need to include such a high refractive index agent There is no. Therefore, it is possible to achieve a high total light transmittance and a low haze value as described above.
  • the high refractive index anti-blocking layer forming composition has a total content of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium-tin oxide of 0.0001% by mass or less in the composition. Is preferred. This is because when a high refractive index agent such as a metal oxide is present in the anti-blocking layer, the extensibility and the bending resistance are generally inferior as compared with the resin-only layer.
  • the total light transmittance (T t (%)) is calculated by the following equation by measuring the incident light intensity (T 0 ) with respect to the anti-blocking film and the total transmitted light intensity (T 1 ) transmitted through the anti-blocking film. .
  • the haze is calculated from the following formula in accordance with JIS K7105.
  • H Haze (cloudiness value) (%)
  • T d Diffuse transmittance (%)
  • T t Total light transmittance (%)
  • the total light transmittance and the haze value can be measured using, for example, a haze meter (manufactured by Suga Test Instruments Co., Ltd.).
  • the anti-blocking layer formed using the high refractive index anti-blocking layer forming composition of the present invention is characterized by having high extensibility in addition to high hardness and refractive index. Therefore, the anti-blocking film in this invention can be used suitably in preparation of the film which has a transparent conductive layer which comprises a touchscreen etc., for example.
  • a transparent conductive layer and an optical interference layer for controlling the reflectance by optical interference can be used in combination in an appropriate order as necessary depending on the application.
  • the order in which the transparent conductive layer, the optical interference layer, and the high-refractive index anti-blocking layer are stacked is not particularly limited as long as it fulfills a function expected to appear depending on the application.
  • the transparent conductive layer is A
  • the optical interference layer is B
  • the high refractive index antiblocking layer to be the subject of the present invention is C
  • the transparent polymer base material is D
  • the present invention when the order of lamination is used as a substrate for a touch panel, the transparent conductive layer is A, the optical interference layer is B, the high refractive index antiblocking layer to be the subject of the present invention is C, the transparent polymer base material is D, and the present invention.
  • the optical interference layer described above refers to a layer that prevents or suppresses reflected light by appropriately combining a high refractive index layer and a low refractive index layer.
  • the optical interference layer is composed of at least one high refractive index layer and at least one low refractive index layer. Two or more combination units of the high refractive index layer and the low refractive index layer may be used.
  • the thickness of the optical interference layer is preferably 30 nm to 150 nm, and more preferably 50 nm to 150 nm.
  • the optical interference layer can be formed by either a wet method or a dry method.
  • a wet method such as a doctor knife, bar coater, gravure roll coater, curtain coater, knife coater, spin coater, etc., spray method, dipping method, etc., dry method such as PVD method such as sputtering method, vacuum deposition method, ion plating method, etc.
  • a printing method, a CVD method, or the like can be applied.
  • a transparent conductive laminate constituting a touch panel or the like is generally a film having a transparent conductive layer.
  • the transparent conductive layer is not particularly limited, but is a crystalline layer containing indium oxide, and more specifically, mainly composed of indium such as ITO (indium-tin oxide) and IZO (indium-zinc oxide).
  • ITO indium-tin oxide
  • IZO indium-zinc oxide
  • a crystalline layer is preferably used.
  • a method for forming the transparent conductive layer there are a PVD method such as a sputtering method, a vacuum deposition method, and an ion plating method, a coating method, a printing method, and a CVD method, and the PVD method or the CVD method is preferable.
  • the transparent conductive layer of the transparent conductive laminate, the anti-blocking layer and the base film may be twisted based on the difference in thermal shrinkage and thermal expansion between the two.
  • the anti-blocking layer provided using the high refractive index anti-blocking layer forming composition of the present invention is characterized by having high visibility and good hardness and high extensibility.
  • the resulting antiblocking layer has high extensibility, so that the antiblocking layer follows well even when the base film is locally thermally expanded by heating in the stage of providing the transparent conductive layer, etc. As a result, there is an advantage that defects such as film warp do not occur.
  • the anti-blocking film in which the transparent polymer substrate on which the high refractive index anti-blocking layer forming composition is coated is a PET film having a thickness of 20 to 300 ⁇ m
  • the thickness of the anti-blocking layer is, for example, 0.05 to 10 ⁇ m.
  • the production of a polymer base film is performed by winding a resin base material in a molten state in a roll shape while being perpendicular to the vertical direction (winding direction: MD direction) and the horizontal direction (TD direction: MD direction).
  • the film is produced by a biaxial stretching method in which a film having a uniform thickness is produced.
  • high stress remains in the MD direction. Therefore, the obtained film tends to cause thermal expansion / shrinkage particularly in the MD direction.
  • Generation of cracks (film cracks) and the like can be effectively verified by performing a test in which the obtained anti-blocking film is stretched in the MD direction, which is the direction wound during the production of the polymer base film. There is an advantage.
  • extension performance of the formed antiblocking layer can be evaluated by verifying the bending resistance of an antiblocking film.
  • Polycarbonate is a material with excellent physical properties such as heat resistance and impact resistance, but especially in the case of a polycarbonate film with a thin film thickness, cracks may occur due to stress such as bending. .
  • a polycarbonate film having a thin film thickness is used as a base film in this way, when the extensibility of the anti-blocking layer formed on the base film is high, by providing an anti-blocking layer, It becomes possible to prevent the occurrence of cracks.
  • the antiblocking layer formed by the high refractive index antiblocking layer forming composition of the present invention has high extensibility. Therefore, there is an advantage that the toughness against bending stress can be improved in an anti-blocking film using a polycarbonate having a thin film thickness as a base film. More specifically, when the transparent polymer base material on which the high refractive index antiblocking layer forming composition is coated is an antiblocking film which is a polycarbonate film having a thickness of 30 to 200 ⁇ m, Even when it is bent 180 ° under the conditions of 60 ° C. and 60 ° C., there is a state in which no cracks are generated in either the antiblocking layer or the substrate.
  • the thickness of the anti-blocking layer is, for example, 0.05 to 10 ⁇ m.
  • the anti-blocking layer formed using the high refractive index anti-blocking layer forming composition of the present invention is characterized by having good anti-blocking performance and hardness, and high visibility and extensibility.
  • the anti-blocking layer formed by the high refractive index anti-blocking layer forming composition of the present invention has a high refractive index. Therefore, even when the anti-blocking layer in the present invention is provided on a substrate film having a high refractive index such as a PET film or a polycarbonate film, there is an advantage that no interference fringes are generated.
  • the antiblocking layer in this invention can be used suitably especially in the film which has a transparent conductive layer which comprises a touchscreen electrode.
  • phenol novolac type epoxy resin solution Metoquinone 1000 ppm and triphenylphosphine 2000 ppm are added to 100 parts by weight of the solid content of the obtained phenol novolac type epoxy resin, and acrylic acid is added dropwise at 100 ° C. until the acid value becomes 1 mgKOH / g or less.
  • a phenol novolac type epoxy acrylate (1) was obtained.
  • the obtained phenol novolak epoxy acrylate (1) had a weight average molecular weight of 950, a hydroxyl value of 140 mgKOH / g, and a refractive index of 1.572.
  • the SP value was 12.7.
  • Example E1 As the component (A), the phenol novolac type epoxy acrylate (1) obtained in Production Example 1 is used, and as the component (B), ethoxylated orthophenylphenol acrylate (acrylate having 1 mol of ethoxy structure in the molecule, viscosity at 25 ° C.
  • a hard coating composition was prepared using 130 mPa ⁇ s and a refractive index of 1.577). The raw materials shown in Table 1 were sequentially mixed at the solid content mass shown in Table 1 and stirred to obtain a hard coating composition.
  • the viscosity measurement of the ethoxylated orthophenylphenol acrylate of the component (B) was obtained by collecting 100 ml of the ethoxylated orthophenylphenol acrylate of the component (B) as a test sample in a glass container and adjusting the temperature to 20 ° C. Using a viscometer (TVB-22L manufactured by Toki Sangyo Co., Ltd.) and M1Rotor, the measurement was performed at a rotation speed of 60 rpm. The refractive index of component (B) was measured using an Abbe refractometer by a method based on JIS K0062.
  • the obtained hard coating composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 12. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet light using an ultraviolet irradiator (manufactured by Fusion) to obtain a PET film and a hard coat film having a 6.5 ⁇ m thick hard coat layer.
  • KEFW Teijin DuPont 188 ⁇ m optical PET film
  • the obtained hard coating composition was dropped onto a Teijin Chemicals 100 ⁇ m optical PC film (Pure Ace) and coated using a bar coater # 9. After coating, it was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet rays with an ultraviolet irradiator (manufactured by Fusion) to obtain a hard coat film having a polycarbonate film and a hard coat layer having a thickness of 5.0 ⁇ m.
  • Example E2 to E5 The hard coating composition was changed in the same manner as in Example E1 except that the type and amount of component (A) were changed to those described in Table 1 and pentaerythritol triacrylate was used as the other (meth) acrylates. A product was prepared. Using the obtained hard coating composition, two types of hard coat films were obtained in the same manner as in Example E1.
  • Comparative Examples E6 and E10 With the formulation shown in Table 2, hard coating compositions were prepared as in the examples.
  • the obtained hard coating composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 13. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet light using an ultraviolet irradiator (manufactured by Fusion) to obtain a PET film and a hard coat film having a 6.5 ⁇ m thick hard coat layer. Further, the obtained hard coating composition was dropped onto a 100 ⁇ m optical PC film (Pure Ace) manufactured by Teijin Chemicals and coated using a bar coater # 10. After coating, it was dried at 70 ° C.
  • Comparative Examples E8, E12, E13 With the formulation shown in Table 2, hard coating compositions were prepared as in the examples. The obtained hard coating composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 20. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiation machine (manufactured by Fusion). In the case of using the hard coating composition of Comparative Example E12, a hard coat film having a PET film and a hard coat layer having a film thickness of 6.5 ⁇ m was obtained.
  • KEFW Teijin DuPont 188 ⁇ m optical PET film
  • the coating composition was not cured and a hard coat layer could not be provided. Further, the obtained hard coating composition was dropped onto a 100 ⁇ m optical PC film (Pure Ace) manufactured by Teijin Chemicals and coated using a bar coater # 14. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiation machine (manufactured by Fusion). When the hard coating composition of Comparative Example E12 was used, a hard coat film having a polycarbonate film and a hard coat layer having a thickness of 5.0 ⁇ m was obtained. On the other hand, when the hard coating compositions of Comparative Examples E8 and E13 were used, the coating composition was not cured and a hard coat layer could not be provided.
  • an ITO layer was formed, and a transparent conductive laminate to be a movable electrode substrate was produced.
  • the thickness of the formed ITO layer was about 30 nm, and the surface resistance value after film formation was about 150 ⁇ / ⁇ .
  • the interference fringes of the obtained transparent conductive laminate were not visually recognized.
  • nD 1.3 to 1.7 manufactured by Atago Co., Ltd.
  • nD 1.3 to 1.7 manufactured by Atago Co., Ltd.
  • nD 1.3 to 1.7 manufactured by Atago Co., Ltd.
  • One drop of the intermediate solution was dropped on the sample with a dropper, and the secondary prism was closed.
  • the condition is that air does not enter the intermediate liquid layer.
  • Lamp light was incident on the sub-prism, the measurement knob was turned while looking through the eyepiece, the boundary of the light and darkness of the refractive field was adjusted to the intersection, the value of the scale field was read to 4 digits after the decimal point, and the refractive index was measured.
  • the hardness was measured using a pencil scratch coating film hardness tester (Model P, pressure load 100 g to 1 kg, manufactured by Toyo Seiki Seisakusho).
  • a pencil for pencil scratch test (manufactured by the Japan Paint Inspection Association) manufactured by Mitsubishi Uni was used and adjusted with abrasive paper (3MP-1000) so that the tip of the lead had a smooth and circular cross section.
  • the pencil was fixed so that the scratch angle was 45 °, and the test was performed under the condition of a load of 750 g. For each test, the test was repeated five times while shifting the test location while smoothing the core. The presence or absence of dents on the surface of the coating film was confirmed visually based on the following evaluation criteria.
  • the hardness of the PET film used in the preparation of the hard coat films of Examples and Comparative Examples is HB to F, and the hardness of the polycarbonate (PC) film is 5B to 4B. Therefore, in a hard coat film having a PET film and a hard coat layer, if the hardness is H or more, the hardness is increased by two or more stages, and it is determined that the hard coat layer has sufficient hardness. . Further, in a hard coat film having a polycarbonate film and a hard coat layer, if the hardness is 3B or more, the hardness is increased by two or more steps, and it is determined that the hard coat layer has sufficient hardness. .
  • the elongation was measured using an autograph (AG-1S manufactured by Shimadzu Corporation).
  • a test sample is cut out to 10 mm ⁇ 150 mm, and is sandwiched between upper and lower chucks of the measuring instrument in a direction in which the longitudinal direction of the sample is extended.
  • a sample sample was stretched at a speed of 2 cm / sec under room temperature (20 ° C.) conditions, an elongation rate at which no breakage / crack occurred was obtained.
  • Interference fringe evaluation method Interference fringes (appearance evaluation) The test piece was bonded to a 100 ⁇ 100 mm black acrylic plate using an optical film adhesive so that the coated surface was on the surface. A sample is placed at a distance of 10 cm vertically from the fluorescent tube of a stand-type three-wavelength fluorescent lamp (SLH-399 manufactured by TWINBARD) and visually observed. Visual observation was performed and judged based on the following evaluation criteria.
  • ⁇ Interference fringes (interference patterns) are not visually recognized under a three-wavelength fluorescent lamp, but slightly visible under sunlight
  • ⁇ Interference fringes (interference patterns) are slightly visible
  • ⁇ Interference fringes (interference patterns) Clearly visible
  • the light transmittance of the test piece was measured with an ultraviolet-visible spectrophotometer (UV-2450, manufactured by Shimadzu Corporation)
  • UV-2450 ultraviolet-visible spectrophotometer
  • the transmittance amplitude in the range of 500 to 750 nm was determined based on the following evaluation criteria.
  • ⁇ The difference between the maximum value and the minimum value of the transmittance is less than 0.5%
  • ⁇ The difference between the maximum value and the minimum value of the transmittance is 0.5% or more and less than 1.0%
  • ⁇ The maximum value and the minimum value of the transmittance Difference in value is 1.0% or more
  • I-184 1-hydroxycyclohexyl phenyl ketone, photopolymerization initiator bisphenol A EO-modified diacrylate: manufactured by Toagosei Co., Ltd., Aronix M-211B, bisphenol A EO (2 mol) -modified diacrylate
  • high refractive index filler 1 zirconia ZRMIBK30WT % (Zirconium oxide, manufactured by CIK Nanotech)
  • High refractive index filler 2 Titania TiMIBK15WT% (titanium oxide, manufactured by CIK Nanotech)
  • Bifunctional urethane acrylate NV100: CN-9893 (manufactured by Sartomer) Indicates.
  • Comparative Examples E1 and E2 are examples in which the amount of component (B) is outside the scope of the present invention. In these cases, there was a problem that the hardness of the obtained film was lowered.
  • Comparative Example E3 is an example using a diacrylate having a bisphenol A skeleton instead of the component (A). In Comparative Example 3, the refractive index of the obtained film was lowered, and the occurrence of interference fringes was confirmed. There was also a problem that the hardness was lowered.
  • Comparative Example E4 is an example using acryloylmorpholine instead of component (B). Also in this comparative example E4, the refractive index of the obtained film was lowered, and the occurrence of interference fringes was confirmed. Moreover, the extensibility was also inferior. Comparative Examples E5 to E8 are examples in which zirconia oxide or titanium oxide, which is a high refractive index agent, is used instead of using components (A) and (B). In these comparative examples, while the hardness was good, the extensibility was greatly inferior. The composition of Comparative Example E8 was not cured. Comparative Examples E9 to E13 are examples using bifunctional urethane acrylate for the purpose of imparting extensibility to the hard coat layer. In these comparative examples, although there was an example in which the extensibility was somewhat improved, the balance between hardness and refractive index was poor. Note that the composition of Comparative Example E13 did not cure.
  • the hard coating compositions of Comparative Examples E5 to E13 contain a high refractive index filler.
  • the refractive index itself of the obtained hard coat layer is certainly high.
  • interference fringes are confirmed in any of the hard coat layers obtained in these comparative examples.
  • the reason why the interference fringes were confirmed in these comparative examples is that the resin component forming the hard coat layer has a low refractive index, while a high refractive index filler having a high refractive index is mixed in the resin component. This is probably because of this.
  • FIG. 1 is a graph showing a transmission spectrum (transmittance (%)) in a wavelength range of 400 to 800 nm of a hard coat layer obtained using the hard coating composition of Example E1.
  • FIG. 2 is a graph showing the transmission spectrum (transmittance (%)) in the wavelength range of 400 to 800 nm of the hard coat layer obtained using the hard coating composition of Comparative Example E10.
  • the hard coat layer obtained using the hard coating composition of the present invention has a very small amplitude width in the transmission spectrum and optical blurring in the visible wavelength range. Can be understood.
  • the hard coat layer obtained using the hard coating composition of Comparative Example E10 has a large amplitude width in the transmission spectrum and a large optical blur in the visible wavelength range. Also from these transmission spectrum results, the technical effect of the present invention can be understood for confirmation.
  • the viscosity measurement of the ethoxylated orthophenylphenol acrylate of the component (B) was obtained by collecting 100 ml of the ethoxylated orthophenylphenol acrylate of the component (B) as a test sample in a glass container and adjusting the temperature to 20 ° C. Using a viscometer (TVB-22L manufactured by Toki Sangyo Co., Ltd.) and M1Rotor, the measurement was performed at a rotation speed of 60 rpm. The refractive index of component (B) was measured using an Abbe refractometer by a method based on JIS K0062.
  • the obtained hard coating composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 12. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet light using an ultraviolet irradiator (manufactured by Fusion) to obtain a PET film and a hard coat film having a 6.5 ⁇ m thick hard coat layer.
  • KEFW Teijin DuPont 188 ⁇ m optical PET film
  • the obtained hard coating composition was dropped onto a Teijin Chemicals 100 ⁇ m optical PC film (Pure Ace) and coated using a bar coater # 9. After coating, it was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet rays with an ultraviolet irradiator (manufactured by Fusion) to obtain a hard coat film having a polycarbonate film and a hard coat layer having a thickness of 5.0 ⁇ m.
  • Example F2 to F4 The hard coating composition was changed in the same manner as in Example 1 except that the type and amount of component (A) were changed to those shown in Table 3 and pentaerythritol triacrylate was used as the other (meth) acrylates. A product was prepared. Using the obtained hard coating composition, two types of hard coat films were obtained in the same manner as in Example 1. In Example F4, Ogsol EA-F5503 (manufactured by Osaka Gas Chemical Co., Ltd.) was used as the component (C).
  • Comparative Examples F1 and F2 With the formulation shown in Table 4 , hard coating compositions were prepared as in the examples. Using the obtained hard coating composition, two types of hard coat films were obtained in the same manner as in Example F1.
  • an ITO layer was formed, and a transparent conductive laminate to be a movable electrode substrate was produced.
  • the thickness of the formed ITO layer was about 30 nm, and the surface resistance value after film formation was about 150 ⁇ / ⁇ .
  • the interference fringes of the obtained transparent conductive laminate were not visually recognized.
  • Example E6 The same evaluation as in Example E6 was performed on the hard coat films obtained in Examples F1 to F4 and Comparative Examples F1 and F2. The evaluation results are shown in Table 3 and Table 4.
  • I-184 1-hydroxycyclohexyl phenyl ketone, a photopolymerization initiator.
  • any of the hard coating films having a hard coat layer formed using the hard coating compositions of Examples F1 to F4 had no generation of interference fringes and had a high refractive index and good hardness. . Furthermore, the obtained hard coating film had high extensibility and bending resistance.
  • Comparative Example F1 is an example in which the amount of component (A) and component (C) is less than the range in the present invention. In Comparative Example F1, the film extensibility and flex resistance were inferior.
  • Comparative Example F2 is an example in which the amount of component (A) is less than the range in the present invention and the amount of component (C) exceeds the range in the present invention. In Comparative Example F2, there was a problem that the hardness of the obtained film was lowered. From the results of these Examples and Comparative Examples, it can be seen that an excellent interference fringe suppressing effect is achieved in the hard coat layer obtained by the present invention.
  • FIG. 3 is a graph showing a transmission spectrum (transmittance (%)) in the wavelength range of 400 to 800 nm of the hard coat layer obtained using the hard coating composition of Example F1.
  • the hard coat layer obtained by using the hard coating composition of the present invention has a very small amplitude width in the transmission spectrum and small optical blur in the visible wavelength range. Understandable. Also from these transmission spectrum results, the technical effect of the present invention can be understood for confirmation.
  • Example G1 As the first component, the unsaturated double bond-containing acrylic copolymer (I) obtained in Production Example 3 was used.
  • the component (A) of the second component the phenol novolac type epoxy acrylate (1) obtained in Production Example 1 is used, and as the component (B), ethoxylated orthophenylphenol acrylate (acrylate having 1 mol of ethoxy structure in the molecule,
  • An anti-blocking layer forming composition was prepared using a viscosity at 25 ° C. of 130 mPa ⁇ s, a refractive index of 1.577, and an SP value of 10.6).
  • the raw materials shown in Table 1 were sequentially mixed at the solid content mass shown in Table 5 and stirred to obtain an anti-blocking layer forming composition.
  • the viscosity measurement of the ethoxylated orthophenylphenol acrylate of the component (B) was obtained by collecting 100 ml of the ethoxylated orthophenylphenol acrylate of the component (B) as a test sample in a glass container and adjusting the temperature to 20 ° C. Using a viscometer (TVB-22L manufactured by Toki Sangyo Co., Ltd.) and M1Rotor, the measurement was performed at a rotation speed of 60 rpm. The refractive index of component (B) was measured using an Abbe refractometer by a method based on JIS K0062.
  • the SP value of the second component was calculated as a weight average with respect to the SP value and content of each component such as the component (A), the component (B), and other components contained in the second component.
  • the obtained antiblocking layer-forming composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 12. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a PET film and an antiblocking layer having a thickness of 6.5 ⁇ m.
  • the obtained anti-blocking layer-forming composition was dropped onto a Teijin Chemicals 100 ⁇ m optical PC film (Pure Ace) and coated using a bar coater # 9. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet rays using an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a polycarbonate film and an antiblocking layer having a thickness of 5.0 ⁇ m.
  • Examples G2 to G5 The type and amount of component (A) were changed to those described in Table 5 and pentaerythritol triacrylate (SP value: 12.7) was used as another (meth) acrylate contained in the second component. Except for the above, an anti-blocking layer forming composition was prepared in the same manner as in Example G1. Two types of anti-blocking films were obtained using the obtained anti-blocking layer-forming composition in the same manner as in Example G1.
  • an anti-blocking layer forming composition was prepared in the same manner as Example G1.
  • the obtained antiblocking layer-forming composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 13. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a PET film and an antiblocking layer having a thickness of 6.5 ⁇ m.
  • the obtained anti-blocking layer forming composition was dropped onto a 100 ⁇ m optical PC film (Pure Ace) manufactured by Teijin Chemicals and coated using a bar coater # 10. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet rays using an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a polycarbonate film and an antiblocking layer having a thickness of 5.0 ⁇ m.
  • an anti-blocking layer forming composition was prepared in the same manner as Example G1.
  • the obtained antiblocking layer-forming composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 16. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a PET film and an antiblocking layer having a thickness of 6.5 ⁇ m.
  • the obtained anti-blocking layer forming composition was dropped on a Teijin Chemicals 100 ⁇ m optical PC film (Pure Ace) and coated using a bar coater # 12. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet rays using an ultraviolet irradiator (manufactured by Fusion) to obtain an antiblocking film having a polycarbonate film and an antiblocking layer having a thickness of 5.0 ⁇ m.
  • Comparative Examples G8, G12, G13 With the formulation shown in Table 6, an anti-blocking layer forming composition was prepared in the same manner as Example G1. The obtained antiblocking layer-forming composition was dropped onto a Teijin DuPont 188 ⁇ m optical PET film (KEFW) and coated using a bar coater # 20. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiation machine (manufactured by Fusion). In the case of using the anti-blocking layer forming composition of Comparative Example G12, an anti-blocking film having a PET film and an anti-blocking layer with a film thickness of 6.5 ⁇ m was obtained.
  • KEFW Teijin DuPont 188 ⁇ m optical PET film
  • the coating composition was not cured and an anti-blocking layer could not be provided. Further, the obtained anti-blocking layer forming composition was dropped onto a Teijin Chemicals 100 ⁇ m optical PC film (Pure Ace) and coated using a bar coater # 14. After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ ultraviolet rays with an ultraviolet irradiation machine (manufactured by Fusion).
  • an ITO layer was formed, and a transparent conductive laminate to be a movable electrode substrate was produced.
  • the thickness of the formed ITO layer was about 30 nm, and the surface resistance value after film formation was about 150 ⁇ / ⁇ .
  • the interference fringes of the obtained transparent conductive laminate were not visually recognized.
  • Example E1 The same evaluation as in Example E1 was performed on the antiblocking films obtained in Examples G1 to G5 and Comparative Examples G1 to G13. Anti-blocking (AB) performance was also evaluated as described below. The evaluation results are shown in Table 5 and Table 6.
  • I-184 1-hydroxycyclohexyl phenyl ketone, photopolymerization initiator bisphenol A EO modified diacrylate: manufactured by Toagosei Co., Ltd., Aronix M-211B, bisphenol A EO (2 mol) modified diacrylate, SP value 11.3
  • Acryloylmorpholine SP value 11.9
  • Bifunctional urethane acrylate NV100: CN-9893 (manufactured by Sartomer), SP value 11.1
  • High refractive index filler 1 Zirconia ZRMIBK30WT% (zirconium oxide, manufactured by CIK Nanotech)
  • High refractive index filler 2 Titania TiMIBK15WT% (titanium oxide, manufactured by CIK Nanotech) Indicates.
  • the anti-booking film having an anti-blocking layer formed using the anti-blocking layer forming composition of the example has a good anti-blocking performance, no generation of interference fringes, and a high refractive index, It had good hardness. Furthermore, the obtained anti-booking film had high extensibility and bending resistance.
  • Comparative Examples G1 and G2 are examples in which the amount of component (B) is outside the scope of the present invention. In these cases, there was a problem that the hardness of the obtained film was lowered.
  • Comparative Example G3 is an example in which diacrylate having a bisphenol A skeleton is used instead of component (A). In Comparative Example G3, the refractive index of the obtained film was lowered, and generation of interference fringes was confirmed.
  • Comparative Example G4 is an example using acryloylmorpholine instead of component (B). Also in this comparative example G4, the refractive index of the obtained film was lowered, and the occurrence of interference fringes was confirmed. Moreover, the extensibility was also inferior. Comparative Examples G5 to G8 are examples in which zirconia oxide or titanium oxide, which is a high refractive index agent, is used instead of using components (A) and (B). In these comparative examples, while the hardness was good, the antiblocking property and the extensibility were greatly inferior. Note that the composition of Comparative Example G8 was not cured.
  • Comparative Examples G9 to G13 are examples using bifunctional urethane acrylate for the purpose of imparting extensibility to the anti-blocking layer.
  • the anti-blocking property was inferior, and although the extensibility was somewhat improved, the balance between the hardness and the refractive index was poor.
  • the composition of Comparative Example G13 was not cured.
  • the anti-blocking layer forming compositions of Comparative Examples G5 to G13 contain a high refractive index filler. By including the high refractive index filler, the refractive index itself of the obtained anti-blocking layer is certainly high.
  • the anti-blocking layers obtained in these comparative examples are confirmed to have interference fringes.
  • the reason why interference fringes have been confirmed in these comparative examples is that the resin component forming the anti-blocking layer has a low refractive index, while a high refractive index filler having a high refractive index is mixed in the resin component. This is probably because of this. For this reason, even if the refractive index itself of the anti-blocking layer is increased, the resin component having a low refractive index has an adverse effect, and it is considered that an excellent interference fringe generation suppressing effect cannot be obtained.
  • the transparent hard coat layer formed by the hard coating composition of the present invention is characterized by having good hardness and high visibility and extensibility.
  • the transparent hard coat layer formed by the hard coating composition of the present invention has a high refractive index. Therefore, even when the transparent hard coat layer in the present invention is provided on a base film having a high refractive index such as a PET film or a polycarbonate film, interference fringes are not generated and high extensibility is achieved. There is an advantage that.
  • the anti-blocking layer formed by the anti-blocking layer-forming composition of the present invention is characterized by having excellent anti-blocking performance and good hardness, high visibility and extensibility.
  • the anti-blocking layer formed by the anti-blocking layer forming composition of the present invention is further characterized by having a high refractive index. Therefore, even when the anti-blocking layer in the present invention is provided on a base film having a high refractive index such as a PET film or a polycarbonate film, there is an advantage that no interference fringes are generated.

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PCT/JP2013/057891 2012-03-30 2013-03-19 Composition de revêtement dur et composition de formation d'une couche anti-adhérente à indice de réfraction élevé Ceased WO2013146482A1 (fr)

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US14/388,927 US9938426B2 (en) 2012-03-30 2013-03-19 Hard coating composition and composition for forming a high refractive index antiblocking layer
CN201380028193.5A CN104487524B (zh) 2012-03-30 2013-03-19 硬质涂层组合物及高折射率抗粘连层形成组合物
KR1020147030463A KR102066759B1 (ko) 2012-03-30 2013-03-19 하드 코팅 조성물 및 고굴절률 안티블로킹층 형성 조성물

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JP2012079755A JP5925011B2 (ja) 2012-03-30 2012-03-30 ハードコーティング組成物
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US20170276840A1 (en) * 2015-07-17 2017-09-28 Dai Nippon Printing Co.,Ltd. Layered body for optical member and image display device

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WO2013146483A1 (fr) * 2012-03-30 2013-10-03 帝人株式会社 Stratifié électroconducteur transparent
JP5490954B1 (ja) 2013-09-30 2014-05-14 日本ビー・ケミカル株式会社 導電性積層体およびそれを用いるタッチパネル
JP5490955B1 (ja) 2013-09-30 2014-05-14 帝人株式会社 導電性積層体およびそれを用いるタッチパネル
JP6491394B2 (ja) * 2016-03-30 2019-03-27 日本ペイント・オートモーティブコーティングス株式会社 成形加飾用積層フィルム
WO2017187805A1 (fr) * 2016-04-28 2017-11-02 富士フイルム株式会社 Feuille conductrice de capteur tactile, corps stratifié de capteur tactile, capteur tactile et panneau tactile
CN109313286B (zh) * 2016-07-28 2020-11-03 株式会社Lg化学 用于保护起偏振器的光学膜、包括其的偏光板和图像显示装置
CN110023795B (zh) * 2016-10-07 2021-06-29 日涂汽车涂料有限公司 光学层叠部件

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US20170276840A1 (en) * 2015-07-17 2017-09-28 Dai Nippon Printing Co.,Ltd. Layered body for optical member and image display device
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